Molecules 2015, 20, 7528-7557; doi:10.3390/molecules20057528 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Review Recent Developments in the Suzuki-Miyaura Reaction: 2010–2014
Irene Maluenda and Oscar Navarro *
Department of Chemistry, University of Sussex, Brighton BN1 9QJ, UK
* Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +44-1273-678734; Fax: +44-1273-876687.
Academic Editor: John Spencer
Received: 17 March 2015 / Accepted: 13 April 2015 / Published: 24 April 2015
Abstract: The Suzuki-Miyaura reaction (SMR), involving the coupling of an organoboron reagent and an organic halide or pseudo-halide in the presence of a palladium or nickel catalyst and a base, has arguably become one of most utilized tools for the construction of a C-C bond. This review intends to be general account of all types of catalytic systems, new coupling partners and applications, including the literature between September 2010 and December 2014.
Keywords: Suzuki-Miyaura; palladium; nickel; N-heterocyclic carbene; phosphine; polymerization
1. Introduction
Since its discovery in 1979 [1], the Suzuki-Miyaura reaction (SMR) [2–5], involving the coupling of an organoboron reagent and an organic halide or pseudo-halide in the presence of a palladium or nickel catalyst and a base, has arguably become one of most utilized tools for the construction of a C-C bond. The reaction follows an oxidative addition transmetallation reductive elimination catalytic cycle that benefits from the use of electron-donating, sterically demanding ligands which promote first and last steps [2]. Clear advantages over other palladium-catalyzed cross-coupling reactions [5] include: (i) mild reaction conditions; (ii) ready availability of organoboron reagents, which also are inert to water and related solvents, as well as oxygen, and generally thermally stable; (iii) tolerant toward various functional groups; and (iv) low toxicity of starting materials and by-products [6]. These features have allowed researchers to utilize it in a wide variety of applications, from natural product synthesis to the development of polymeric materials. Due to its impact in such a variety of fields, Akira Suzuki, Molecules 2015, 20 7529 together with Richard F. Heck and Ei-Ichi Negishi, was awarded in September 2010 the Nobel Prize in Chemistry “for palladium-catalyzed cross couplings in organic synthesis”. Since then, excellent and thorough reviews covering specific aspects of this reaction have been published: a historical account [7], and reviews focusing on Ni-catalyzed reactions [8], nanocatalysts [9], preformed Pd catalysts [10], sulphur-containing ligands [11,12], and the coupling of polyhalogenated heteroarenes [13]. This review intends to be a more general account of all types of catalytic systems, new coupling partners and applications, including the literature between September 2010 and December 2014. It is worth pointing out that a Scopus search on the topic “Suzuki coupling” lead to more than 3000 articles during that period; therefore, only a selection of the most significant developments and applications of the SMR are presented in here. In addition and for simplicity, details on the specifics of the reaction conditions (base, solvent, temperature) have been omitted unless any of those factors where determinant to the outcome, focusing mostly in coupling partners, ligands, metals and products.